Catalytic carbonylation of three and four membered heterocycles

ABSTRACT

Epoxides, aziridines, thiiranes, oxetanes, lactones, lactams and analogous compounds are reacted with carbon monoxide in the presence of a catalytically effective amount of catalyst having the general formula [Lewis acid] z+ {[QM(CO) x ] w− } y  where Q is any ligand and need not be present, M is a transition metal selected from the group consisting of Groups 4, 5, 6, 7, 8, 9 and 10 of the periodic table of elements, z is the valence of the Lewis acid and ranges from 1 to 6, w is the charge of the metal carbonyl and ranges from 1 to 4 and y is a number such that w times y equals z, and x is a number such as to provide a stable anionic metal carbonyl for {[QM(CO) x ] w− } y  and ranges from 1 to 9 and typically from 1 to 4.

CROSS-REFERENCE TO RELATED APPLICATION

[0001] This application claims the benefit of U.S. ProvisionalApplication No. 60/336,170, filed Dec. 6, 2001, the whole of which isincorporated herein by reference.

FIELD OF INVENTION

[0002] This invention is directed to catalytic carbonylation ofepoxides, aziridines, thiiranes, oxetanes, lactones, lactams andanalogous compounds.

BACKGROUND OF THE INVENTION

[0003] Poly((R)-β-hydroxybutyrate), i.e., R—PHB, a naturally occurringthermoplastic polyester, shares many of the physical and mechanicalproperties of poly(propylene) but unlike polypropylene is biodegradable.Despite proven properties and ready applications, industrial productionof R—PHB as a bulk polymer using biological methods has, to date, proveneconomically non-viable. Potential alternate synthetic routes to thispromising polymer include Baeyer-Villiger oxidation of an isotacticpropylene/carbon monoxide copolymer, asymmetric hydrogenation of theunsaturated polyester from ring opening polymerization (ROP) of ketenedimer, and ROP of (R)-β-butyrolactone (R—BBL). The first two routesinvolve post-polymerization modification of a polymer backbone, adifficult and unreliable task. The third route uses the proventechnology of lactone polymerization but presently the starting materialR—BBL is not a readily available commodity such as would be required forcommercial polymer production. Thus, for commercial production of R—PHBby the third route, there is a need for an efficient, effective,inexpensive process for producing R—BBL.

[0004] The approach with the most promise for producing R—BBL is thecatalytic synthesis of R—BBL from R-propylene oxide and carbon monoxide.R-Propylene oxide is readily available through Jacobsen's hydrolytickinetic resolution as described in Tokunaga, M., et al., Science 277,936-938 (1997).

[0005] Drent, E., et al. European Patent Application No. 0577206 isdirected to a process for the carbonylation of expoxides by reactionwith carbon monoxide at elevated pressure and temperature in thepresence of a catalyst system comprising a source of cobalt and ahydroxy substituted pyridine compound. Data is presented in Example 5 ofEuropean Patent Application No. 0577206 where reaction pressurized to 60bar carbon monoxide at 75° C. for 6 hours, is indicated to give 93%conversion of propylene oxide with a selectivity of greater than 90%into β-butyrolactone (BBL). However, Lee, T. L., et al., J. Org. Chem.65, 518-521 (1999) and inventors herein were unable to produce theresults of Drent and rather obtained low (15%) yields of BBL andsignificant amounts of undesired oligomeric by-products.

[0006] Lee, T. L., et al., J. Org. Chem. 64, 518-521 describes thecarbonylation of propylene oxide using 900 psi CO at 80° C. indimethoxyethane using a mixture of [Ph₃P═N═PPh₃][Co(CO)₄] and BF₃.EtO asa catalyst to obtain a yield of 77% BBL (some α-methyl-β-propiolactonealso was produced) in a 24 hour reaction. This result leaves room forconsideration of other catalyst systems.

SUMMARY OF THE INVENTION

[0007] It has been found herein that the catalytic activity of thecatalyst system used for carbonylation of epoxides is mediated bymodification of the cation therein and that use of a cationic Lewis acidas the cation in the catalyst system provides a novel approach. Whilethe BF₃ in the catalyst of Lee et al. is a Lewis acid, it is a neutralLewis acid. The cation in the Lee et al. catalyst system is[Ph₃P═N═PPh₃]⁺ which is not a Lewis acid. It is possible that a cationicLewis acid is formed in situ in the reaction described in Drent et al.European Patent Application No. 0577206. The instant invention does notembrace the Drent et al. catalytic system or any catalyst formedtherefrom and in one subset embraces only formation of cationic Lewisacid extrinsic to the carbonylation reaction and charging substrate andcatalyst and then reacting with carbon monoxide under pressure.

[0008] In a preferred embodiment herein, the catalyst system providesvery high yields in short reaction time (e.g., yields greater than 95%BBL or R—BBL in less than 2{fraction (1/2)} hours).

[0009] Furthermore, it has been found that the catalyst system herein isuseful not only for carbonylation of R-propylene oxide and propyleneoxide but also for carbonylation of analogs of these and also forcarbonylation of corresponding four membered heterocycles. BBL and saidcarbonylation products of analogs may be polymerized to form polymerswhich may be used as additives to R—PHB to modify the propertiesthereof. Furthermore, resulting chiral lactones, lactams, thiolactones,γ-lactones and anhydrides, etc. are useful in organic synthesis.

[0010] An invention of one embodiment herein, denoted the firstembodiment, is directed to a process for carbonylation of a compoundhaving the formula:

[0011] where R₁, R₂, R₃ and R₄ are selected from the group consisting ofhydrogen, C₁-C_(100,000)-alkyl, C₂-C_(100,000)-alkenyl andC₆-C_(1000,00)-aryl, where the alkyl, alkenyl and aryl are optionallysubstituted with halogen or benzyl ether, and alkylaryl, ester, ketone,alcohol, acid, aldehyde, amide and tosyl containing from 1 to 20 carbonatoms, and benzyl ether, alkyl substituted silyl ether where the ethergroup is C₁-C₆ alkylene and where the alkyl substitution consists of oneto three C₁-C₆ alkyl(s) substituted on silyl, and any otherfunctionality that the catalyst referred to below is tolerant of, andwhere where R₂ and R₄ can join to from a ring, and X is selected fromthe group consisting of O, S and NR₅ where R₅ is selected from the groupconsisting of hydrogen, C₁-C_(100,000)-alkyl, C₂-C_(100,000)-alkenyl andC₆-C_(100,000)-aryl where the alkyl, alkenyl and aryl are optionallysubstituted with halogen or benzyl ether, and alkylaryl, ester, ketone,alcohol, acid, aldehyde, amide and tosyl containing from 1 to 20 carbonatoms and benzyl ether, alkyl substituted silyl ether where the ethergroup is C₁-C₆-alkylene and where the alkyl substitution consists of oneto three C₁-C₆ alkyl(s) substituted on silyl, and any otherfunctionality that the catalyst referred to below is tolerant of anddoes not cause rearrangement and where n is 0 or 1, and Y is C═O or CH₂,said process comprising the step of reacting compound (I) with carbonmonoxide in the presence of a catalytically effective amount of catalysthaving the general formula [Lewis acid]^(z+){[QM(CO)_(x)]^(w−)}_(y)where Q is any ligand and need not be present, M is a transition metalselected from the group consisting of transition metals of Groups 4, 5,6, 7, 8, 9 and 10 of the periodic table of elements and z is the valenceof the Lewis acid and ranges from 1 to 6, w is the charge of the metalcarbonyl and ranges from 1 to 4 and is usually 1, y is a number suchthat w times y equals z and x is a number such as to provide a stableanionic metal carbonyl for {[QM(CO)_(x)]^(w−)}_(y) and ranges from 1 to9 and typically from 1 to 4, to form a product having the structuralformula:

[0012] where R₁, R₂, R₃ and R₄ and X correspond to R₁, R₂, R₃, R₄ and Xin (I) including R₂ and R₄ forming a ring if that is the case for (I),and in the case where n for (I) is 0, n for (II) is 0 or 1, and in thecase where n for (I) is 1, n for (II) is 1; said catalyst excludingcatalyst formed from the combination of a cobalt source and a hydroxysubstituted pyridine.

[0013] The alkyls include branched as well as straight chain alkyls.C₁-C_(100,000)alkyl, C₂-C_(100,000)alkenyl and C₆-C_(100,000)aryl usedin the definition of R₁, R₂,R₃, R₄ and R₅ allow for the heterocyclesbeing pendant to polymers; where the heterocycles are not pendant topolymers, the range for alkyl can be, for example C₁-C₂₀, the range foralkenyl can be, for example, C₂-C-₂₀, and the range for the aryl can be,for example, C₆-C₂₀.

[0014] The term “halogen” includes fluorine, chlorine, iodine andbromine.

[0015] The term “any other functionality that the catalyst referred tobelow is tolerant of” is used herein to mean that the functionality canbe present without causing the catalyst to be inactive.

[0016] The term “does not cause rearrangement” excludes the case whereone or more moieties, particularly R₅, become part of or the ring thatis formed, e.g., in the case where R₅ is benzoyl as is demonstratedbelow, or otherwise change the order of connectivity inherent in thestarting heterocycle excluding the insertion of C═O functionality asdefined above.

[0017] The term “such as to provide a stable anionic metal carbonyl for{[QM(CO)_(x)]^(w−)}_(y)” is used herein to mean that{[QM(CO)_(x)]^(w−)}_(y) is a species characterizable by analyticalmeans, e.g., NMR, IR, X-ray crystallography, Raman spectroscopy and/orelectron spin resonance (EPR) and isolable in catalyst form as the anionfor a Lewis acid cation or a species formed in situ, excluding thosethat may result from the combination of a cobalt source, carbon monoxideand hydroxy substituted pyridines as set forth in Drent et al. EuropeanPatent Application No. 0577206.

[0018] In a subset of the invention of the first embodiment of theinvention herein, at least one of R₁, R₂, R₃ and R₄ is not hydrogen.

[0019] In the subset of the first embodiment of the invention where nfor (I) is 0 and n for (II) is 1, epoxide or analog is doublycarbonylated, arriving at the resultant anhydride or analog without thenecessity of isolating the intermediate lactone or analog, thusproviding a so called “one pot” reaction.

[0020] In a subset of the invention of the first embodiment of theinvention herein, the catalyst is added catalyst, i.e., is not formed insitu in the carbonylation reaction.

[0021] A preferred catalyst has the structural formula:

[0022] where So is tetrahydrofuran and ^(t)Bu is t-butyl and M is Al orCr. This catalyst where M is Al is referred to herein as Catalyst (G).

[0023] Another preferred catalyst has the structured formula:

[0024] where THF is tetrahydrofuran and ^(t)Bu is t-butyl and M is Al orCr. Thus catalyst where M is Al is referred to as catalyst (E¹).

[0025] Still another preferred catalyst has the structural formula:

[0026] where So is tetrahydrofuran and ^(t)Bu is t-butyl. This catalystis referred to as catalyst (H).

[0027] Still another preferred catalyst has the structural formula:

[0028] where So is tetrahydrofuran and Ph is phenyl. This catalyst isreferred to as catalyst (J).

[0029] Still another preferred catalyst has the structural formula:

[0030] where M is titanium with a valence of three. This catalyst isreferred to as catalyst (G¹).

[0031] Still another preferred catalyst has the structured formula:

[0032] where M is samarium with a valence of three. This catalyst isreferred to as catalyst (G²).

[0033] Another embodiment of the invention denoted the second embodimentis directed to the case where the compound carbonylated has thestructural formula:

[0034] where Ph is phenyl, and the process comprises the step ofreacting compound (XI) with carbon monoxide in the presence of acatalytically effective amount of catalyst having the general formula[Lewis acid]^(z+){[QM(CO)_(x)]^(w−)}_(y) where Q is any ligand and neednot be present, M is a transition metal selected from the groupconsisting of transition metals of Groups 4, 5, 6, 7, 8, 9 and 10 of theperiodic table of elements and z is the valence of the Lewis acid andranges from 1 to 6, w is the charge of the metal carbonyl and rangesfrom 1 to 4, and y is a number such that w times y equals z and x is anumber such as to provide a stable anionic metal carbonyl for{[QM(CO)_(x)]^(w−)}_(y) and ranges from 1 to 9 and typically from 1 to4, to form a product which comprises a mixture of:

[0035] The compound (XI) has the structural formula (I) where n is 0, Xis NR₅ and R₅ is benzoyl. In this case R₅ participates in rearrangementwhereby the carbonyl of R₅ becomes part of the ring of the product andthe Ph of R₅ becomes directly bonded to the ring of the product.

[0036] A third embodiment of the invention is directed to novelcatalysts useful for carbonylation reactions of the first and secondembodiments of the invention.

[0037] One genus of novel catalysts for the third embodiment comprisescompounds having the structural formula:

[0038] where ^(t)Bu is t-butyl and M is Al or Cr and So is a neutral twoelectron donor. A preferred catalyst of this genus has the structuralformula (V) where M is Al and the neutral two electron donor istetrahydrofuran and is referred to as catalyst (G).

[0039] Another genus of novel catalysts for the third embodimentcomprises compounds having the structural formula:

[0040] where ^(t)Bu is t-butyl and So is a neutral two electron donor. Apreferred catalyst of this genus has the structural formula (VIII) wherethe neutral two electron donor is tetrahydrofuran and is referred to ascatalyst (B).

[0041] Another genus of novel catalysts for the third embodimentcomprises compounds having the structural formula:

[0042] where ^(t)Bu is t-butyl and So is a neutral two electron donor. Apreferred catalyst of this genus has the formula (IX) where the neutraltwo electron donor is tetrahydrofuran and is referred to as catalyst(F).

[0043] Also included in the third embodiment is the compound having thestructural formula:

[0044] where ^(t)Bu is t-butyl, THF is tetrahydrofuran and M is Al. Thiscompound is referred to as catalyst (E¹).

[0045] Another genus of novel catalysts for the third embodimentcomprises compounds having the structural formula:

[0046] where ^(t)Bu is t-butyl and So is a neutral two electron donor. Apreferred catalyst of this genus has the structural formula (X) wherethe neutral two electron donor is tetrahydrofuran and is referred to ascatalyst (H).

[0047] Still another genus of novel catalysts for the third embodimentcomprises compounds having the structural formula:

[0048] where Ph is phenyl and So is a two electron donor. A preferredcatalyst of this genus has the structural formula (XI) where the neutraltwo electron donor is tetrahydrofuran and is referred to as catalyst(J).

[0049] Further variation of metal and ligand architecture will beobvious to those skilled in the art.

BRIEF DESCRIPTION OF THE DRAWINGS

[0050]FIG. 1 shows NMR data for Catalyst (G); the y-axis for the figureis arbitrary intensity.

DETAILED DESCRIPTION

[0051] We turn now to the compound to be carbonylated in the firstembodiment which has the formula:

[0052] where R₁, R₂, R₃ and R₄ arc selected from the group consisting ofhydrogen, C₁-C_(100,000)-alkyl, C₂-C_(100,000)-alkenyl andC₆-C-_(100,000)-aryl, where the alkyl, alkenyl and aryl are optionallysubstituted with halogen or benzyl ether, and alkylaryl, ester, ketone,alcohol, acid, aldehyde, amide and tosyl containing from 1 to 20 carbonatoms and benzyl ether, alkyl substituted silyl ether where the ethergroup is C₁-C₆ alkylene and where the alkyl substitution consists of oneto three C₁-C₆ alkyl(s) substituted on silyl and any other functionalitythat the catalyst referred to below is tolerant of, and where R₂ and R₄can join to form a ring and X is selected from the group consisting ofO, S and NR₅ where R₅ is selected from the group consisting of hydrogen,C₁-C_(100,000)-alkyl, C₂-C_(100,000)-alkenyl, and C₆-C_(100,000)-alkylwhere the alkyl, alkenyl and aryl are optionally substituted withhalogen or benzyl ether, and alkylaryl, ester, ketone, alcohol, acid,aldehyde, amide and tosyl containing from 1 to 20 carbon atoms, andbenzyl ether, alkyl substituted silyl ether where the ether group isC₁-C₆-alkylene and where the alkyl substitution consists of one to threeC₁-C₆ alkyl(s) substituted on silyl, and any other functionality thatthe catalyst referred to below is tolerant of and does not causerearrangement and where n is 0 or 1, and Y is C═O or CH₂.

[0053] We turn now to the examples of compound (I) where n is 0 and X isO, i e, which are epoxides. The compound (I) of most interest herein isR-propylene oxide, i.e., compound (I) where X is O and R₁ is H, R₂ is H,R₃ is (R)-Me and R₄is H, since carbonylation of that compound hereinprovides R—BBL. Other monocyclic epoxide compounds (I) herein include,for example, ethylene oxide (compound (I) where n is 0 and X is O and R₁is H, R₂ is H, R₃ is H and R₄ is H), propylene oxide (compound (I) wheren is 0 and X is O and R₁ is H, R₂ is H, R₃ is Me and R₄ is H); 1-buteneoxide which also may be named 1,2-epoxybutane (compound (I) where n is 0and X is O and R₁ is H, R₂ is H, R₃ is Et and R₄ is H); 1-heptene oxide(compound (I) where n is 0 and X is O and R₁ is H, R₂ is H, R₃ is C₅H₁₁and R₄ is H); isobutylene oxide (compound (I) where n is 0 and X is Oand R₁ is H, R₂ is H, R₃ is Me and R₄ is Me); 2,3-epoxybutane (compound(I) where n is 0 and X is O and R₁ is H, R₂ is Me, R₃ is Me and R₄is H);epichlorohydrin (compound (I) where n is 0 and X is O and R₁ is H, R₂ isH, R₃ is CH₂Cl and R₄ is H); and epibromohydrin (compound (I) where n is0 and X is O and R₁ is H, R₂ is H, R₃ is CH₂Br and R₄is H);1,2-epoxy-5-hexene (compound (I) where n is 0 and X is O and R₁ is H, R₂is H, R₃ is H and R₄ is —(CH₂)₂CH═CH₂); and benzyl glycidyl ether whichhas the formula:

[0054] i.e., compound (I) where R₁ is H, R₂ is H, R₃ is CH₂OCH₂Ph and R₄is H. Examples of bicyclic epoxides for compound (I) include, forexample, cyclohexene oxide (compound (I) where R₁ is H, R₃ is H, and R₂and R₄ from —(CH₂)—₄, cyclopentene oxide (compound (I) where R₁ is H, R₃is H and R₂ and R₄ form —(CH₂)₃—, cyclooctene oxide (compound (I) whereR₁ is H, R₃ is H and R₂ and R₄ form —(CH₂)₆—) and cyclododecene oxide(compound (I) where R₁ is H, R₃ is H and R₂ and R₄ form —(CH₂)₁₀—).These monocyclic and bicyclic epoxides are all available commercially.

[0055] We turn now to examples of compound (I) where n is 0 and X is NR₅where R₅ is selected from the group consisting of C₁-C_(100,000)-alkyl,C₂-C_(100,000)-alkenyl and C₆-C_(100,000)-aryl, where the alkyl, alkenyland aryl are optionally substituted with halogen or benzyl ether, andalkylaryl, ester, ketone, alcohol, acid, aldehyde, amide and tosylcontaining from 1 to 20 carbon atoms and benzyl ether, alkyl substitutedsilyl ether where the ether group is C₁-C₆-alkylene and where the alkylsubstitution consists of one to three C₁-C₆ alkyl(s) substituted onsilyl, and any other functionality that the catalyst referred to belowis tolerant of and does not cause rearrangement. These compounds areaziridines. These include ethyl ethyleneimine, also denoted2-ethylaziridine, (compound (I) where n is 0 and X is NH, R₁ is H, R₂ isH, R₃ is Et and R₄ is H) which is commercially available. Otheraziridines useful herein, which are commercially available, are listedin Aldrichimica Acta 2001, 34(2); these arecis-2,3-diphenyl-1-propylaziridine;trans-2,3-diphenyl-1-propylaziridine;cis-1-isopropyl-2,3-diphenylaziridine;trans-1-isopropyl-2,3-diphenylaziridine; 2-methylaziridine;cis-1,2,3-triphenylaziridine; 1-azridineethanol; 1-benzyl 2-methyl(S)-(−)-1,2-aziridinecarboxylate;(S)-(+)-2-benzyl-1-(p-tolylsulfonyl)aziridine; methyl(S)-(−)-1-trityl-2-aziridinecarboxylate; and trimethylolpropanetris(2-methyl-1-aziridinepropionate). Another aziridine useful herein is1-benzyl-2-methylaziridine, i.e., compound (I) where n is 0 and X isNCH₂(C₆H₅), R₁ is H, R₂ is H, R₃ is H and R₄ is Me; this compound can bemade as described in Piotti, M. E., et al, J. Am. Chem. Soc. 118,111-116 (1996). Still another aziridine useful herein is7-benzyl-7-azabicyclo[4.1.0]heptane; i.e., compound (I), where n is 0and X is NCH₂(C₆H₅), R₁ is H, R₃ is H and R₂ and R₄ are linked by—(CH₂)₄—; this compound is made in Background Example 1 hereinafter.Still another aziridine useful herein is 1-tosyl-2-methylaziridine(compound (I) where X is NOS(═O)₂C₇H₈, R₁ is H, R₂ is H, R₃ is H and R₄is Me; this compound is made is Background Example 2 hereinafter. Stillanother aziridine useful herein iscis-1-benzyl-2-(tert-butyldimethylsilyloxymethyl)-3 aziridine (compound(I) where X is NH, R₁ is CH₂C₅H₅, R₂ is H, R₃ is H and R₄ isCH₂OSi(CH₃)₂[C(CH₃)₃]; this compound is made as described in Piotti, M.E., et al., J. Am. Chem. Soc. 118, 111-116 (1996). Other aziridinesuseful herein are available through well established synthetic routes,for example, from epoxides via ring opening with a primary amine andring closure with ethyl diazoacetate or from alkanes with R—N═N—R′ usinga copper catalyst.

[0056] We turn now to examples of compounds (I) where n is 0 and X is S.These compounds are thiiranes. Thiiranes useful herein that arecommercially available include aliphatic thiiranes that are commerciallyavailable in gram to kilogram quantities, e.g., propylene sulfide,epithiochlorohydrin and isobutylene sulfide. A number of otherfunctionality substituted (i.e., esters, acids, amides, ketones, etc.)thiiranes are also available although many of those only in sub-gramquantities.

[0057] We turn now to examples of compounds (I) where n is 1 and X is Oand Y is CH₂. These compounds are oxetanes. An oxetane useful herein hasthe structure (I) where n is 1 and Y is CH₂ and R₁, R₂, R₃ and R₄ are Hand is denoted oxetane and is available commercially. Other oxetanes arecommercially available or can be made by standard procedures in thechemical literature.

[0058] We turn now to examples of compounds (I) where X is O, n is 1 andY is C═O. These compounds are lactones. Lactones useful herein includethose having the structure (I) where X is O, n is 1 and Y is C═O whereR₁, R₃ and R₄ are H and R₂ is Me, Et or CCl₃ or where R₁, R₂ and R₄ areH and R₃ is Me or Ph; these compounds are available commercially. Otherlactones can be made by the process described herein or as described inreferences cited in Mahadevan, V., et al, Angew. Chem. Int. Ed. 41, No.15, 2781-2784 (2002) and Getzler, Y. D. Y. L., et al, J. Am. Chem. Soc.124, No. 7, 1174-1175 (2002).

[0059] We turn now to examples of compounds (I) where X is NR₅, n is 1and Y is C═O. These compounds are denoted lactams. These compounds arecommercially available or can be made by the process outlined herein orby other processes described in the chemical literature.

[0060] Compounds (I) where X is NR₅, n is 1 and Y is CH₂ are azetidines.The compound where R₅ is H, n is 1, Y is CH₂ and R₁, R₂, R₃ and R₄ are His commercially available. Others can be synthesized.

[0061] Compounds (I) where X is S, n is 1 and Y is C═O are thiolactones.Synthesis of some of these can be carried out as described in thechemical literature.

[0062] Compounds (I) where X is S, n is 1 and Y is CH₂ are thietanes.The compound where X is S, n is 1, Y is CH₂ and R₁, R₂, R₃ and R₄ are H,is commercially available. Others can be synthesized.

[0063] We turn now to the processing conditions for the method of thefirst embodiment, i.e., the step of reacting the compound (I) withcarbon monoxide in the presence of a catalytically effective amount ofcatalyst having the general formula [Lewisacid]^(z+){[QM(CO)_(x)]^(w−)}_(y) where Q is any ligand and need not bepresent, M is a transition metal selected from the group consisting ofGroups 4, 5, 6, 7, 8, 9 and 10 of the periodic table of elements, z isthe valence of the Lewis acid and ranges from 1 to 6, for example is 1or 2, w is the charge of the metal carbonyl and ranges from 1 to 4 andusually is 1 and y is a number such that w times y equals z, and x is anumber such as to provide a stable anionic metal carbonyl for{[QM(CO)_(x)]^(w−)}_(y) and ranges from 1 to 9 and typically from 1 to4.

[0064] The reaction equation is:

[0065] where R₁, R₂, R₃, R₄, X, Y and n are as defined above.

[0066] The reaction is carried out at a temperature ranging from 0° C.to 120° C., preferably from 40 to 80° C.

[0067] The mole ratio of CO to compound (I) should be at least 1:1because of stoichiometry.

[0068] The reaction can be driven by a high concentration of CO. One wayof accomplishing a high concentration of CO is to use high pressure CO,i.e., an amount of CO to impart a pressure ranging from 100 to 10,000psi, preferably from 75 to 1,200 psi.

[0069] We turn now to the reaction catalyst. As indicated above, thereaction catalyst has the general formula [Lewisacid]^(z+){[QM(CO)_(x)]^(w−}) _(y) where Q is any ligand and need not bepresent, M is a transition metal selected from the group consisting oftransition metals of Groups 4, 5, 6, 7, 8, 9 and 10 of the periodictable of elements, z is the valence of the Lewis acid and is 1 or 2, wis the charge of the metal carbonyl and ranges from 1 to 4 and usuallyis 1 and y is a number such that w times y equals z and x is a numbersuch as to provide a stable anionic metal carbonyl for{[QM(CO)_(x)]^(w−)}_(y) and ranges from 1 to 9 and typically from 1 to4.

[0070] As indicated above, the catalyst in one subset is referred to asadded catalyst. The term “added” means that the catalyst is formedextrinsic to the carbonylation reaction and is charged to the reactionbefore, during or after pressurization.

[0071] We turn now to the [Lewis acid]^(z+), i.e., to the cationic Lewisacid portion of the catalyst. The term “Lewis acid” is used to mean anelectron pair acceptor that can combine with a molecule or ion that isan electron pair donor forming either covalent or coordinative bond(s),and the term “cationic Lewis acid” is used to mean a Lewis acid that hasone or more positive charges. Preferably, the cationic Lewis acidportion of the catalyst contains a metal, e.g., aluminum or chromium,and a neutral two electron donor which is coordinatively or covalentlybound to the metal. The neutral two electron donor has the function offilling the coordination valence of the cationic Lewis acid. In thecatalysts B, E¹, E², F, G, H and J made herein, the neutral two electrondonor is tetrahydrofuran (THF) and is an artifact from the catalystsynthesis. Other neutral two electron donors for the cationic Lewis acidportion of the catalyst besides THF, include, for example, diethylether, acetonitrile, carbon disulfide or pyridine. In the catalystsynthesis, the neutral two electron donor can be provided as thereaction solvent which can be added before or with or after the otherreactants but is preferably added so as not to disturb the air freeenvironment which is preferred for catalyst synthesis. Cationic Lewisacid portion of catalyst without a neutral two electron donor is alsopossible and can be provided by synthesizing the catalyst in a reactionsolvent which is not a neutral two electron donor providing solvent orby heating catalyst where the cationic Lewis portion of catalystcontains a neutral two electron donor.

[0072] We turn now to the anionic portion of the catalyst which is{[QM(CO)_(x)]^(w−)}_(y) where Q is any ligand and need not be present, Mis a transition metal selected from the group consisting of transitionmetals of Groups 4, 5, 6, 7, 8, 9 and 10 of the periodic table ofelements, z is the valence of the Lewis acid and is 1 or 2 or more, w isthe charge of the metal carbonyl and ranges from 1 to 4 and is usually1, y is a number such that w times y equals z and x is a number such asto provide a stable anionic metal carbonyl for {[QM(CO)_(x)]^(w−)}_(y)and ranges from 1 to 9 and typically from 1 to 4. When Q is not present,the metals of Groups 7 and 9 are preferred. The metals of Group 7include, for example, manganese. The metals of Group 9 include cobalt,rhodium and iridium. A very preferred metal M is cobalt. We turn now tothe optional constituent Q which is any ligand; the term “ligand” isused to mean any discrete species that could have existence separatefrom the transition metal M. Suitable constituents Q include, forexample, triphenylphosphine, cyclopentadienyl (Cp), and pentamethylcyclopentadienyl (Cp*). Ligated metal carbonyl anions are readilyaccessible, in one step through well-known chemistry, e.g., by reductionof Co₂(CO)₈ which is commercially available.

[0073] The reaction catalysts are preferably formed in an air-freeenvironment using standard glovebox and Schlenk-type techniques.

[0074] The catalysts where w is 1 and y is equal to z and z is 1 areformed by the reaction of [Lewis acid]-X with [QM(CO)_(x)]—Y where X isany leaving group and Y is a moiety that will form a salt with X or,alternatively, the catalysts where z ranges from 1 to 6, for example is1 or 2, are formed from a redox reaction of [Lewis acid^(m)] andz/2Q₂M₂(CO)_(2x) to form [Lewis acid^((m+z))]^(z+){[QM(CO)_(x)]⁻}_(z)where m is the oxidation state of the metal, z is both the valence ofthe Lewis acid and the number of anions associated with it and rangesfrom 1 to 6, for example is 1 or 2, M is a transition metal selectedfrom the group consisting of transition metals of Groups 4, 5, 6, 7, 8,9 and 10 of the periodic table of elements, and x is the number requiredto form a stable anionic carbonyl for {[QM(CO)_(x)]⁻}_(z). Complexes ofthe type [QM(CO)_(x)]—Y can be made by the reduction of the anionicspecies [QM(CO)_(x)]₂ where Q, M and x are as defined for{[QM(CO)_(x)]⁻}_(z). The species [QM(CO)_(x)]₂ in many cases arecommercially available. Reducing agents include sodium amalgam and asdescribed in Edgell, W. F., et al., Inorg. Chem. 1970, 9, 1932-1933,sodium hydroxide. This method was used in the synthesis of catalyst D(Catalyst Making 3, hereinafter).

[0075] One genus of preferred catalysts herein have the structure:

[0076] where M is a metal such that (VI) is stable where stable meansthat the catalyst remains active for the course of the reaction. M canbe, for example, titanium with a valence of 3 (catalyst (G¹)), samariumwith a valence of 3 (catalyst (G²)), lanthanum with a valence of 3 orhafnium with a valence of 3. Catalyst (G¹) can be made as described inMerola, J. S., et al. Inorg. Chem 28, 2950-2954 (1989) as well asMerola, J. S., et al., Inorg. Chim. Acta 165, 87-90 (1989). Catalyst(G²) can be made as described in Evans, W. J., et al., Inorg. Chem. 24,4620-4623 (1985) as well as, in Evans., W. J., et al., J. Am. Chem. Soc107, 941-946 (1985). Other catalysts (VI) can be made in correspondingfashion.

[0077] Another catalyst herein is catalyst (G) described above. Thesynthesis of catalyst (G) is described in Catalyst Making Example 1hereinafter. Catalyst (G) may be referred to as[(salph)Al(THF)₂][Co(CO)₄] where salph isN,N′-bis(3,5-di-tert-bulylsalicylidene)-1,2-phenylenediamimo.

[0078] Other catalysts for use herein are the catalysts denoted hereinas catalysts B, D, E¹, E², F, H and J.

[0079] Catalyst (B) has the formula:

[0080] where THF is tetrahydrofuran and ^(t)Bu is t-butyl. The synthesisof Catalyst (B) is described in Catalyst Making Example 2 hereinafter.Catalyst (B) was very active but its synthesis as described in CatalystMaking Example 2, has been difficult to replicate. An alternative routeis the route to make catalyst (F) which is described in BackgroundExample 6 hereinafter.

[0081] Catalyst (D) has the formula [Na]⁺[Co(CO)₄]⁻. The synthesis ofCatalyst (D) is described in Catalyst Example 3 hereinafter.

[0082] Catalysts (E¹) and (E²) have the formula:

[0083] where THF is tetrahydrofuran and ^(t)Bu is t-butyl and M is Alfor Catalyst (E¹) and M is Cr for Catalyst (E²). The synthesis ofCatalyst (E¹) is described in Catalyst Making Example 4 hereinafter. Thesynthesis of Catalyst (E²) is described in Catalyst Making Example 5hereinafter.

[0084] Catalyst (F) has the formula:

[0085] where THF means tetrahydrofuran and ^(t)Bu is t-butyl. Thesynthesis of catalyst (F) is described in Catalyst Making Example 6hereinafter.

[0086] Catalyst (H) has the formula:

[0087] where So is tetrahydrofuran and ^(t)Bu is t-butyl. The synthesisof Catalyst (H) is described in Catalyst Making Example 7 hereinafter.

[0088] Catalyst (J) has the formula:

[0089] where So is tetrahydrofuran and Ph is phenyl. The synthesis ofcatalyst (J) is described in Catalyst Making Example 8 hereinafter.

[0090] An example of a catalyst where z is 2 is [(salen)M]²⁺[Co(CO)₄]₂ ⁻where salen is any tetracoordinate dianionic ligand synthesized from adiamine and two equivalents of a 2-hydroxybenzaldehyde, which can bemade from reaction of one equivalent of (salen)Sn^((II)) with oneequivalent of Co₂(CO)₈ and M is a metal. The (salen)Sn^((II)) is readilyobtainable from [(Me₃Si)₂N]₂ Sn and (salen)H₂ where (salen)H₂ is theprotonated form of the ligand as shown in Kuchta, et al., J. C. S.Dalton Trans. 20, 3559 (1999).

[0091] For the catalysts [Lewis acid]^(z+){[QM(CO)_(x)]^(w−)}_(y), otherLewis acids besides what are illustrated above and their synthesis, willbe obvious to those skilled in the art.

[0092] The mole ratio of compound (I) charged to catalyst charged, canrange, for example, from 1:1 to 10,000:1 and preferably is 100:1 to2,000:1 and the best ratio envisioned is 1,000:1. A mole ratio of 100:1was found to give the best conversions but approximately 1,800:1 givesmuch better activity.

[0093] We turn now to the solvent for the reaction. The reaction may becarried out neat, i.e., without added solvent and where the compound (I)is the reaction vehicle to reduce waste disposal requirements as well asto simplify purification. If the reaction is not carried out neat, itmay be carried out in diglyme, triglyme, dimethoxyethane (denoted DMEhereinafter), or preferably in tetrahydrofuran, or may be carried out inany solvent in which catalyst, substrate and product are all soluble.

[0094] In the case where the compound (I) is a monocyclic epoxide and asingle carbonyl is introduced, the reaction product of interest is aβ-lactone. The terminology “β-lactone” is because the lactone can beformed by dehydrative lactonization of a β-hydroxy acid. In the casewhere the epoxide is bicyclic, there is no common name such as β-lactoneand IUPAC would name the product according to bicyclic nomenclature. Forexample, the product of the carbonylation of cyclohexene oxide would becalled 7-oxa-bicyclo[4.2.0]octan-8-one. The products of carbonylation ofcyclooctene oxide and cyclododecene oxide are respectively called9-oxa-bicyclo[6.2.0]decan-10-one and13-oxa-bicyclo[10.2.0]tetradecan-14-one and are products made incarbonylation Examples XLI and XLII and are embodiments of the inventionherein.

[0095] In the case where the compound (I) is a monocyclic aziridine anda single carbonyl is introduced, the reaction product of interest is aβ-lactam.

[0096] In the case where the compound (I) is a monocyclic oxetane, thereaction product of interest is a γ-lactone.

[0097] In the case where the compound (I) is a monocyclic thiirane and asingle carbonyl is introduced, the reaction product of interest is athiolactone.

[0098] In the case where the compound (I) is a monocyclic lactone, thereaction product of interest is a cyclic acid anhydride.

[0099] In the case of the compound (I) where X is NR₅, n is 1 and Y isCH₂ and the compound (I) is monocyclic, i.e., where the compound (I) isa monocyclic azetidine, the reaction product of interest is a γ-lactam.

[0100] In the case of the compound (I) where X is NR₅, n is 1 and Y isC═O and the compound (I) is monocyclic, i.e., where the compound (I) isa monocyclic β-lactam, the reaction product of interest is a2,5-pyrrolidinedione.

[0101] In the case where the compound (I) where X is S, n is 1 and Y isC═O and the compound is monocyclic, i.e., where the compound (I) is amonocyclic thiolactone, the reaction product of interest is a cyclicanhydrosulfide.

[0102] In the case of the compound (I) where X is S, n is 1 and Y is CH₂and the compound (I) is monocyclic, i.e., where the compound (I) is amonocyclic thietane, the reaction product of interest is γ-thiolactone.

[0103] The yield of product of interest is determined from twocomponents, i.e., the percent of compound (I) consumed, and the percentselectivity which is product of interest as a percentage of allproducts, and the percent conversion times percent selectivity givesyield percent. The yield percents obtained were related to catalyst andcompound (I). For propylene oxide and R-propylene oxide, catalyst (G)give percents conversion of 95% with selectivity greater than 99%. Forpropylene oxide, Catalyst (B) gives percent conversion of 99% andpercent selectivity greater than 99%.

[0104] The time of reaction is a parameter affecting percent yield. Ingeneral, times of reaction can range, for example, from 15 minutes to 96hours. The preferred time of reaction for Catalyst (G) is one-half to 2and one-half hours except where compound (I) was epichlorohydrin a timeof 8-12 hours was more appropriate.

[0105] We turn now to the case where n for (I) is 0 and n for (II) is 1,and epoxide or analog is doubly carbonylated arriving at the resultantanhydride without the necessity of isolating the intermediate lactone oranalog, thus providing a so-called “one pot” reaction. The reactioncondition mainly affecting this is time of reaction. In other words,sufficient time is provided for a first carbonylation reaction toproceed to a finish whereupon sufficient further time is provided forthe second carbonylation to be effected. Also reaction temperature, molepercent catalyst, catalyst used, substrate used and solvent, couldinfluence conversion and selectivity.

[0106] The β-lactone products can be converted to polymers with metalalkoxide catalysts. See R, L. R., et al, J. Am. Chem. Soc. 2002, paperaccepted for publication. See also Muller, H. M., et al., Angew. Chem.Int. Ed. Engl. 1993, 32, 477-502 and references cited therein. See alsothe following in respect to polymerization of β-lactones: Kurcok, P., etal., Macromolecules 1992, 25, 2017-2020; Hori, Y., et al.,Macromolecules 1993, 26, 5533-5534; Le Borgne, A., et al., Macromol.Rapid Commun. 1994, 15, 955-960; Lenz, R. W., et al., Can. J. Microbiol.1995, 41, 274-281; Cheng, M., et al., J. Am. Chem. Soc. 1998, 120,11018-11019; and Schechtman, L. A., et al., J. Polym. Prepr. (Am. Chem.Soc., Div. Polym. Chem.) 1999, 40(1), 508-509.

[0107] The utility of the product from polymerization of R—BBL, namelyR—PHB, is described above. Copolymers with lactones other than R—BBLgive the ability to mediate the properties of the resultant polymer,e.g., plasticity, barrier properties and rate of degradation. Thelactones, particularly chiral lactones, are also useful as syntheticintermediates in organic chemistry (e.g., see Gellman, S. H., Chem. Res.31, 173 (1988); and Seebach, D., et al., Chem. Commun. 2015 (1997) whichrefers to chiral lactones as aldol analogs.

[0108] The lactam products can he converted to polymers with metal anionor metal amide catalysts. The polymers are called poly(lactam)s and havealso been called poly-beta-peptides, and have been discussed in theliterature as “biomimetic materials.” See, for example, Magriotis, P.A., Angew. Chem. Int. Ed. Engl. 2001, Vol. 40, 4377-4379.

[0109] Products from polymerization of lactams, have utility, forexample, for drug delivery. The lactams themselves may be used inantibiotics.

[0110] The thiolactone products (also called 4-alkyl-thietan-2-ones) canbe converted to polymers or copolymers. For example, a copolymer of BBLand 3-mercaptopropionate (the thiolactone from the carbonylation ofethylene sulfide) can be prepared; the copolymer has modified propertiesfrom those of poly(β-hydroxybutyrate).

[0111] The γ-lactone and anhydride products for carbonylation ofcompound (I) where n=1 and analogs thereof have utility for the field ofchemistry.

[0112] We turn now to the second embodiment of the invention hereinwhich is directed to a process for the carbonylation of a compoundhaving the formula:

[0113] said process comprising the step of reacting compound (XI) withcarbon monoxide in the presence of a catalytically effective amount ofcatalyst having the general formula [Lewisacid]^(z+){[QM(CO)_(x)]^(w−)}_(z) where Q is any ligand and need not bepresent, M is a transition metal selected from the group consisting oftransition metals of Groups 4, 5, 6, 7, 8, 9 and 10 of the periodictable of elements and z is the valence of the Lewis acid and ranges from1 to 6, for example is 1 or 2, w is the charge of the metal carbonyl andranges from 1 to 4 and is usually 1 and y is a number such that w timesy equals z and x is a number such as to provide a stable anionic metalcarbonyl for {[QM(CO)_(x)]^(w−)}_(y). The reaction is carried out at acarbon monoxide pressure ranging from 100 to 10,000 psi, preferably from75 to 1,200 psi and a temperature ranging from 0° C. to 120° C.,preferably from 40 to 80° C., in the presence of catalyst in a moleratio of the compound (XI) to catalyst ranging from 1:1 to 10,000:1,preferably from 100:1 to 2000:1, for example over a time period rangingfrom 15 minutes to 96 hours. The catalysts useful for the secondembodiment are the same as those useful for the first embodiment. Thepreferred catalyst for use in the second embodiment has been found to beCatalyst (G¹). The product comprises a mixture of the two isomericoxazinones, namely 4-methyl-2-phenyl-4,5-dihydro-[1,3] oxazin-6-onewhich has the formula:

[0114] and 5-methyl-2-phenyl-4,5-dihydro-[1,3] oxazin-6-one which hasthe formula:

[0115] Thus, the benzoyl substituent on the aziridine participates inrearrangement to introduce the benzoyl into the ring of the productwhere the oxygen of the benzoyl becomes a ring atom and the double bondof the carbonyl of the benzoyl becomes part of the ring and the phenylof the benzoyl is directly bonded to a ring carbon atom.

[0116] We turn now to the third embodiment of the invention herein.Catalysts the same as catalyst (B), (E¹), (F), (G), (H) and (J) but withdifferent neutral two electron donor from THF can be prepared the sameas the corresponding catalysts with THF by synthesizing the catalyst bymethod comprising adding source of different neutral two electron donor(e.g., diethyl ether, acetonitrile, carbon disulfide or pyridine)instead of THF for reaction of [Lewis acid]-X and [QM(CO)_(x)]—Y in thegeneral reaction described above.

[0117] The following background Examples 1 and 2 illustrate thesynthesis of compound (I) for use in the Reaction Examples XXIII andXXIV. The following Catalyst Synthesis Examples 1-8 illustrate making ofthe catalysts used in Reaction Examples and synthesis of catalysts ofthe third embodiment herein. Catalyst (H) used in Reaction Examples wasmade as described in Merola, J. S., et al., Inorg. Chem. 28, 2950-2954(1989). Catalyst (J) used in a Reaction Examples hereinafter was made asdescribed in Evans, W. J., et al, Inorg. Chem. 24, 4620-4623 (1985).

[0118] The following working Examples I-XLIII and associated tables,illustrate the methods herein.

Background Example 1 Synthesis of 7-Benzyl-7-Azabicyclo[4.1.0]heptane

[0119] a) Synthesis of 2-Benzylamino-cyclohexanol. To a solution ofcyclohexene oxide (5 g, 51 mmol) in 10 ml CH₃CN, anhydrous LiClO₄, (5.44g., 51 mmol) was added and stirred until complete dissolution of thesalt occurred. The resulting solution was treated with the requiredamount of benzylamine (5.5 g, 51 mmol) at room temperature withstirring. The reaction mixture was then stirred for 24 h at roomtemperature. At the end of the reaction, 100 ml water was added and thesolution stirred for 30 min, extracted into diethyl ether (3×25) andfinally crystallized from hot hexanes. (5.0 g, 50% yield).

[0120]¹H NMR (CDCL₃, 300 MHz): δ0.93-1.10(1H, m), 1.18-1.33 (4H, m),1.71 (2H, m), 2.05 (1H, m), 2.15 (1H, m), 2.31 (1H, m), 3.20 (1H, m),3.35 (1 h, br), 3.68 (1H, d, J=12.9 Hz), 3.95 (1H, d, J=13.0 Hz),7.23-7.35 (5H, m).

[0121] b) Cyclization of 2-Benzylamino-cyclohexanol. Diethylazodicarboxylate (Aldrich, 95%, 3.6 ml, 22.6 mmol) was slowly added toan ether solution (50 ml) of 2-benzylaminio-cyclohexanol (3.1 g, 15mmol) and PPh₃ (5.94 g, 22.6 mmol) under N₂, with stirring, in anice-bath. After addition, the ice bath was removed, and the mixturestirred at room temperature for 36 h. The resulting crystallineprecipitate was filtered and the solvent removed from the filtrate byrotary evaporation to yield the crude product, which was purified bycolumn chromatography (petroleum ether: diethyl ether=50:50) (2.1 g, 75%yield).

[0122]¹H NMR (CDCl₃, 300 MHz): δ1.31 (4H, m), 1.63 (2H, m), 1.83 (4H,m), 3048 (2H, s), 7.31 (5H, m).

Background Example 2 Synthesis of 2-Methyl-1-Tosyl-Aziridine

[0123] 2-Methylaziridine (3.6 ml, 51 mmol) was added to a 10% aqueousKOH solution (30 ml) and cooled in an ice bath for 30 min. To thissolution p-toluenesulfonyl chloride (9.9 g, 52 mmol) was added rapidlywhile maintaining the temperature below 4° C. The resulting mixture wasstirred for 30 min at 0° C., then stirred at room temperature overnight.The white precipitate was washed multiple times with cold water anddried under vacuum. The washed product was dissolved in hot petroleumether and allowed to crystallize at 0° C., yielding colorless crystals(6.3 g, 57 % yield).

[0124]¹H NMR (CDCl₃, 300 MHz): δ1.26 (3H, d, J=6.0), 2.02 (1H, d, J=4.5Hz), 2.44 (3H, s), 2.58 (1H, d, J=6.9 Hz), 2.82 (1H, m), 7.31 (2H, d,J=8.1 Hz), 7.80 (2H, d, J=8.1 Hz).

Catalyst Synthesis Example 1 Synthesis of Catalyst (G)

[0125] All manipulations were performed with strict air-free techniques.All reagents and solvent were dried and degassed prior to use. In adrybox, N,N′-bis(3,5-di-tert-butylsalicylidene)-1,2-phenylenediamine(1.38 g, 2.55 mmol) was placed in a Schlenk tube equipped with astir-bar and an air-free addition funnel charged with diethyl aluminumchloride (Aldrich, 1.8 M in toluene) (1.42 ml, 2.5 mmol). Upon removalto the bench top, the ligand was dissolved in 20 ml of CH₂Cl₂, giving apale orange solution. Dropwise addition of diethyl aluminum chloridesolution at room temperature resulted in considerable evolution of gas,which was vented, and a yellowing of the solution. After rinsing of theaddition funnel several times with CH₂Cl₂, the solution was stirred for8.5 hours during which a copious amount of yellow precipitate formed. Invacuo solvent removal gave a yellow solid which was rinsed 3-4 timeswith hexanes (10-20 ml) and then pumped down. The Schlenk tube wasbrought into a drybox where white powdery sodium cobalt tetracarbonyl(0.49 g, 2.53 mmol), stored at −35° C. under nitrogen, was added. Uponremoval to the bench and addition of tetrahydrofuran (30 ml) at roomtemperature, the solution immediately turned a deep red. The foilwrapped tube stirred for two days and was concentrated to 5-10 ml,layered with hexanes (50 ml) and left to sit for a day. Significantamounts of yellow and white precipitates as well as masses of X-rayquality red crystals formed. The red crystals were the desired product,Catalyst (G). The impurities were easily washed away with repeatedrinses of hexanes allowing isolation of pure catalyst[(salph)Al(THF)₂][Co(CO)₄], (G) (2.10 g, 93% yield).

[0126]¹H NMR (C₆D₆, 300 MHz) δ9.53 (s, HC═N), 8.35 (s, HAr), 8.14 (s,HAr), 7.92 (s, HAr), 7.50 (s, HAr), 7.16 (s, HC₆D₅), 3.23 (s, O—CH₂),1.70 (s, C(CH₃)₃), 1.46 (s, C(CH₃)₃), 0.83 (s, OCH₂CH₂), spectrum shownin FIG. 1. IR (KBr): v_(co)=1885 cm⁻¹.

[0127] Crystal data: triclinic, a=12.0136(6) Å, b=13.2447(7) Å,c=15.2876(8) Å, α=101.560(1)°, β=91.506(1)°, γ=90.295(1)°, V=2382.1(2)Å³, space group P-1; Z=2, formula weight 880.91 forC₄₀H₄₆AlCoN₂O₄.2C₄H₈O and density (calc.)=1228 g/ml; R(F)=0.0553 andRw(F)=0.1474 (I>2σ(I)).

Catalyst Synthesis Example 2 Synthesis of Catalyst (B)

[0128] In a glovebox, a Schlenk tube was charged with 2.58 g (4.73 mmol)(R,R)-(−)-N,N′-bis(3,5-di-tert-butylsalicylaldehyde)-1,2-cyclohexanediamine,0.615 g (5.01 mmol) of chromium (II) chloride (Strem, 99.9% anhydrous,used as received) and a teflon-coated magnetic stir-bar. THF wascanulated in and the reaction was left stir for 6 hours at which pointit was opened to the air and left to stir for 12 hours. The resultantcloudy brown-red solution was rinsed into a separatory funnel with 500ml tert-butyl methyl ether, washed four times with 300 ml saturatedammonium chloride and four times with 300 ml saturated sodium chloride.The solution was dried with sodium sulphate, rotovaped to a red solidand recrystallized from acetonitrile to give 1.33 g (43% yield) of largered diamond shaped crystals Compound (C) which were characterized by IRand X-ray crystallography. Compound (C) was determined to have thestructure:

[0129] In a glovebox, a Schlenk tube was charged with 1.03 g (0.80mmol), Compound C, 0.32 g (1.65 mmol) NaCo(CO)₄(Catalyst(D)) and ateflon-coated magnetic stir-bar. THF was canulated in, the tube wascovered in foil and the solution was left to stir for three days atwhich time it was concentrated in vacuao. Hexanes were layered on top ofthe dark red solution and the solution was left to sit for six day,although crystals had began to form within a day. A flocculentyellowish-white precipitate was separated from the large red blocks ofcrystals by repeated washing with hexanes. Isolation gave 1.14 g (88%yield) of pure Catalyst (B) which was characterized by IR and X-raycrystallography.

Catalyst Synthesis Example 3 Synthesis of Catalyst (D)

[0130] Catalyst (D) was synthesized as described in Edgell, W. F., etal., Inorg. Chem. 1970, 9, 1932-1933.

Catalyst Synthesis Example 4 Synthesis of Catalyst (E¹)

[0131] Synthesis of Catalyst (E¹) differs from that of CatalystSynthesis Example 1 in one aspect only; in this synthesis(R,R)-(−)-N,N′-bis(3,5-di-tert-butylsalicylaldehyde)-1,2-cyclohexanediaminewas used instead ofN,N′-bis(3,5-di-tert-butylsalicylaldehyde)-1,2-phenylenediamine.

Catalyst Synthesis Example 5 Synthesis of Catalyst (E²)

[0132] In a glovebox, a Schlenk tube was charged with 0.64 g (1.06 mmol)(R,R)-(−)-N,N′-bis(3,5-di-tert-butylsalicylaldehyde)-1,2-cyclohexanediaminochromium(III) chloride (Aldrich), 0.21 g (1.06 mmol) NaCo(CO)₄ (Catalyst (D))and a teflon-coated magnetic stir-bar. THF was canulated in, the tubewas covered in foil and the solution was left to stir for two days atwhich time it was concentrated in vacuo. Hexanes were layered on top ofthe dark red solution and the solution was left to sit for six day,although crystals had began to form within a day. A flocculentyellowish-white precipitate was separated from the large red blocks ofcrystals by repeated washing with hexanies. Isolation gave 0.52 g (60%yield) of pure Catalyst (E²) which was characterized by IR and X-raycrystallography.

Catalyst Synthesis Example 6 Synthesis of Catalyst (F)

[0133] In a glovebox, a Schlenk tube was charged with 0.28 g (0.51 mmol)N,N′-bis(3,5-di-tert-butylsalicylaldehyde)-1,2-phenylenediamine, 0.21 g(5.18 mmol) sodium hydride and a teflon-coated magnetic stir-bar. THFwas canulated in with considerable ebullition. The headspace was removedand the solution was stirred at 50° C. for 22 hours at which point theexcess sodium hydride was filtered off, using air-free technique, andthe solution added to a Schlenk tube charged with 0.07 g (0.55 mmol)chromium (II) chloride and a teflon-coated magnetic stir-bar. Theheadspace was removed and the solution heated at 50° C. for 6 hours atwhich point the dark brown solution was filtered, to remove any NaCl,into a Schlenk tube charged with 0.09 g (0.26 mmol) dicobalt octcarbonyland a teflon-coated magnetic stir-bar and stirred for 24 hours. Thevolume of solution was reduced in vacuo and hexanes layered on top.After two weeks the dark red crystals were isolated canulating off themother liquor and washing the remaining material with copious amounts ofhexanes resulting in the isolation of 0.26 g (70% yield) of Catalyst (F)which was characterized by IR and X-ray crystallography.

Catalyst Synthesis Example 7 Synthesis of Catalyst (H)

[0134] This catalyst was made essentially the same as Catalyst (G)(Catalyst Synthesis Example 1) except that the starting material was4,5-dimethyl-[N,N′-bis(3,5-di-tert-butylsalicylidenene)]-1,2-phenylenediamine.

Catalyst Synthesis Example 8 Synthesis of Catalyst (J)

[0135] The catalyst was made essentially the same as Catalyst (E¹)(Catalyst Synthesis Example 5), except that the starting material was(TPP) CrCl where TPP means tetraphenylporphyrin (TPP) CrCl iscommercially available.

Carbonylation Reaction Examples I-XIII

[0136] Carbonylation reactions within the scope of the invention werecarried out as follows for Examples I-VI. A 100 ml Parr reactor wasdried at 90° C., under vacuum overnight. In a drybox, it was cooled in a−35° C. freezer for at least 1.5 hours and equipped with a smalltest-tube and magnetic stir bar. The test-tube was charged with 0.500 mlof compound (I) as described in Table 1 below, stored at −35° C., andcatalyst as described in Table 1 below and amount thereof as describedin Table 2 below. Upon removal from the drybox, the reactor waspressurized to pressure as described in Table 2 below, placed in apreheated oil bath and the reactor was stirred at temperature as setforth in Table 2 for amount of time as indicated in Table 2 below. Whenthe indicated time had passed, the reactor was cooled in a bath of dryice/acetone until the pressure reached a minimum and then slowly vented.The crude mixture was subjected to NMR analysis. Trapping of ventedgases indicates that only 2-5% of the material is lost. Vented gasescontained the same ratios of compounds (within 3-4%) that remained inthe reactor. Results are set forth in Table 3 below.

[0137] Reaction conditions for the carbonylation reaction of Example VIIwere as follows and also include the conditions set forth in Table 2below for Example VII: Using a gas-tight syringe, dry and degasseddiglyme (20 ml) and propylene oxide (10 ml, 143 mmol) were injected intoa 100 ml Parr pressure reactor equipped with a ball valve and a septumand previously charged, in a glovebox, with Catalyst (B) (0.13 g, 0.08mmol). The reactor was pressured up to 1020 psi with carbon monoxide andstirred via the attached impeller at 75° C. for 21 hours at which pointit was cooled to 3° C. in an ice bath and vented.

[0138] Reaction conditions for the carbonylation reaction of ExampleVIII were as follows and also included the conditions set forth in Table2 below for Example VIII: Using an air-free graduated cylinder, 20 ml(285 mmol) propylene oxide was canulated into the above mentioned Parrreactor charged as above with 0.25 g (0.16 mmol) Catalyst (B). Thereactor was pressured up to 810 psi with carbon monoxide and stirred atroom temperature (22° C.) for 16 hours at which point it was cooled inan ice bath and vented.

[0139] Reaction conditions for the carbonylation reaction of Example IXwere identical to those of Example VII except triglyme was used insteadof diglyme and the scale was different (7 ml triglyme, 3.5 ml (50 mmol)propylene oxide, 0.15 g (0.09 mmol) Catalyst (B)) with the additionaldifferences as set forth in Table 2 below.

[0140] Reaction conditions for the carbonylation reaction of Example Xwere identical to those of Example VIII except for the use of 0.07 g(0.09 mmol) Catalyst (B) and except for the differences set forth inTable 2 below.

[0141] Reaction conditions for the carbonylation reaction of Example XIwere identical to those of Example VIII except for the use of 0.08 g(0.10 mmol) Catalyst (E²) in place of Catalyst (B) and except for thedifferences set forth in Table 2 below.

[0142] Reaction conditions for the carbonylation reaction of Example XIIwere identical to those of Example VIII except for the use of 5 ml (71mmol) propylene oxide and 0.05 g (0.04 mmol) Catalyst (F) in place ofCatalyst (B) and except for the differences set forth in Table 2 below.

[0143] Results for Examples VII-XII are set forth in Table 3 below.

[0144] The carbonylation reaction for Example XIII was carried out asfollows. A 100 ml Parr reactor equipped with a mechanical stirrer washeated at 80° C., under vacuum, overnight. The reactor was charged withpropylene oxide and catalyst (D), (0.15 M solution in triglyme), in thedrybox. Upon removal from the drybox, the reactor was pressured to 1,000psi with carbon monoxide and heated at 80° C. with stirring for 16hours. The catalyst was used in amount of 2 mole percent Co by weight ofepoxide. After the 16 hours, the reactor was cooled in an ice bath untilthe pressure reached a minimum and then slowly vented. The crude mixturewas subjected to NMR analysis. Catalyst and compound (I) are set forthin Table 1 below. Reaction conditions are set forth in Table 2 below.The results for Example XIII are set forth in Table 3 below.

[0145] The resulting β-lactone products were obtained as crude mixtures.Purification to obtain purified β-lactone products is readily carriedout by vacuum distillation, flash column chromatography or otherstandard purification techniques.

[0146] Table 1 listing the catalyst and compound (I) for each ofExamples I-XIII is set forth below: TABLE 1 Example Catalyst Compound(I) I G R-propylene oxide II G propylene oxide III G 1-butene oxide IV Gepichlorohydrin V G isobutylene oxide VI C 2,3-epoxybutane VII Bpropylene oxide VIII B propylene oxide IX B propylene oxide X  E¹propylene oxide XI  E² propylene oxide XII F propylene oxide XIII Dpropylene oxide

[0147] Table 2 listing for the reaction conditions for each of ExamplesI-XIII, is set forth below: TABLE 2 Compound (I) charged/ Pco T catalystcharged (Co basis) Example time(h) (psi) (° C.) Solvent (mole ratio) I 1880 50 neat 100:1 II 1 880 50 neat 100:1 III 2.5 880 50 neat 100:1 IV9.5 880 50 neat 100:1 V 1 880 50 neat 100:1 VI 7.5 880 75 neat  50:1 VII21 1020 75 diglyme 1800:1  VIII 16 810 22 neat 1800:1  IX 12 870 75triglyme 525:1 X 96 960 75 neat 3300:1  XI 95 940 75 neat 2900:1  XII 4900 80 neat 1800:1  XIII 16 1000 80 triglyme  50:1

[0148] Co basis was used in defining Compound (I) charged/catalystcharged mole ratio because all the catalysts have the common feature ofCo(CO)₄ anion so this provides standardization.

[0149] Table 3 presenting results for Examples I-XIII is set forth belowwhere percent conversion and percent selectivity are as describedpreviously and TON means turnover number and is moles compound (I)consumed divided by moles catalyst charged. TABLE 3 ConversionSelectivity Example (%) (%) TON I 95 >99 95 II 95 >99 95 III 99 >99 99IV 73 >99 73 V 83 >99 83 VI 80 70 40 VII 72 >95 1300 VIII 40 >99 730 IX90 >99 460 X 69 80 2200 XI 52 85 1500 XII 86 96 1600 XIII 52 12 2

[0150] In Example I, the product was R—BBL.

[0151] In Example XIII, 6% acetone and 40% polymer were also produced.

Carbonylation Reaction Examples XIV-XXI

[0152] The carbonylation reactions of these examples were carried out inthe presence of 5 mole % catalyst G (0.2 Mn DME) under a carbon monoxidepressure of 900 psi. In each case the compound (I) was present in amountof 1.92 mmol. The Example number, compound (I), temperature of reaction,time of reaction, product and yield obtained, are listed in Table 4below: TABLE 4 Substrate Temp Time. Example (I) (° C.) (h) ProductsYield % XIV

60 4

95 XV

60 4

95 XVI

60 4

99 XVII

60 4

90 XVIII

60 5

60 XIX

50 3

90 XX

60 10

99 XXI

60 10

75

[0153] The yields were determined by ¹H NMR spectroscopy. Theenantiomeric excess for Example XV was greater than 99%(R)-β-butyrolactone. The results for Examples XIV, XV, XVI, XVII, XVIII,XX and XXI were 100% regioselective, that is the insertion occurred atthe less substituted carbon. In the cases of Examples XIX, insertion atthe more substituted carbon is also present and the two products areshown. In Table 4, the compound (I) for Example XIV is propylene oxide,the compound (I) for Example XV is (R)-propylene oxide, the compound (I)for Example XVI is 1,2-epoxybutane, the compound (I) for Example XVII is1,2-epoxy-5-hexene, the compound (I) for Example XVIII isepichlorohydrin, the compound (I) for Example XIX is isobutylene oxide,the compound (I) for Example XX is cis-2,3-epoxybutane and the compound(I) for Example XXI is trans-2,3-epoxybutane.

Carbonylation Examples XXII-XXV

[0154] The carbonylation reactions of these examples were carried out inthe presence of 5 mole % catalyst (G) and for each substrate also withcatalyst (H) (0.2M in DME) under a carbon monoxide pressure of 900 psi.In each case the compound (I) was present in amount of 1.92 mmol. Theexample number, compound (I), temperature of reaction, time of reaction,product and yield obtained, are listed in Table 5 below: TABLE 5Substrate Temp Time. Yield Example (I) Catalyst (° C.) (h) Products %XXII

G H 60 60 6 6

90 50 XXIII

G H 80 80 18 18 

80 <5 XXIV

G H 90 90 6 6

35 99 XXV

G 60 5

95

[0155] The yields were determined by ¹H NMR spectroscopy. The resultsfor Examples XXII, XXIII and XXIV were 100% regioselective. In the caseof Example XXV, insertion at the more substituted carbon is also presentand the two products are shown in Table 5. In Table 5, Ph is phenyl, Tsis tosyl and TBSO is tert-butyldimethylsilyloxy. The compound (I) forExample XXII is 1-benzyl-2-methyl aziridine, for Example XXIII is7-benzyl-7-azabicyclo[4.1.0]heptane, for Example XXIV is1-tosyl-2-methylaziridine and for Example XXV iscis-1-benzyl-2-(tert-butyldimethylsiloxymethyl)-3-methylaziridine.

Carbonylation Example XXVI

[0156] Oxetane was carbonylated in the presence of 1 mole % catalyst(E¹) under a carbon monoxide pressure of 880 psi, neat, for 1.5 hours at50° C. The product of interest was

[0157] The percent conversion was about 30% (includes product ofinterest and other products).

Carbonylation Example XXVII-XXXVII

[0158] These examples involve carbonylation of β-lactones according tothe following reaction equation:

[0159] The starting materials, reaction conditions and results are givenin Table 6 below. In respect to the starting materials, in each case R₁and R₄ are H. TABLE 6 Catalyst and Time Temp. Conversion Example R₃ R₂its amount Solvent (h) (° C.) % XXVII H Me E¹, 1% DME 5 80 35 XXVIII HMe E¹, 2% DME 5 80 65 XXIX H Me G¹, 5% DME 5 80 60 XXX H Me G¹, 5% DME14 80 >90 XXXI H Me E¹, 1% — 8 80 80 XXXII H Me E¹, 1% — 24 80 84 XXXIIIH Me G², 2% DME 20 50 85 XXXIV H Et G¹, 5% DME 10 80 70 XXXV H CCl₃ G¹,5% DME 24 75 — XXXVI Me H G¹, 5% DME 5 80 95 XXXVII Ph H G¹, 5% DME 1080 80

[0160] In the above table, Me is methyl, Et is ethyl, Ph is phenyl andDME is dimethoxyethane.

Carbonylation Example XXXVIII

[0161] The compound (I) was benzyl glycidyl ether. The benzyl glycidylether was carbonylated in the presence of 1 mole % catalyst (H), neat,under a carbon monoxide pressure of 800 psi for 15 hours at 50° C.

Carbonylation Example XXXIX, XL and XLI

[0162] For Example XXXIX, the compound (I) was 1-buteneoxide. ForExample XL the compound (I) was 1-heptene oxide. For Example XLI, thecompound (I) was cyclooctene oxide. In each case the compound (I) wascarbonylated in the presence of 0.4 mole % catalyst (J), neat, under acarbon monoxide pressure of 1,000 psi for 20 hours at 60° C. The productof Carbonylation Example XLI was 9-oxa-bicyclo[6.2.0]decan-10-one andhas the structure:

Carbonylation Example XLII

[0163] The compound (I) was cyclododecene oxide. The cyclododecene oxidewas carbonylated in the presence of 1.67 mole % catalyst (G), neat,under a carbon monoxide pressure of 1400 psi for 6 hours at 50° C. Theproduct was 13-oxa-bicyclo[10.2.0]tetradecan-14-one and has thestructure:

Carbonylation Example XLIII

[0164] The compound (I) was:

[0165] The compound (I) was carbonylated in the presence of 5 mole %catalyst (G¹), in dimethoxyethane under a carbon monoxide pressure of900 psi for 4 hours at 50° C. The reaction product was a mixture of thetwo isomeric oxazinones:

[0166] 4-Methyl-2-phenyl-4,5-dihydro-[1,3]oxazin-6-one

[0167] 5-Methyl-2-phenyl-4,5-dihydro-[1,3]oxazin-6-one

[0168] Variations

[0169] Many variations will be obvious to those skilled in the art.Thus, tie scope of the invention is defined by the claims.

What is claimed is:
 1. A process for the carbonylation of a compoundhaving the formula:

where R₁, R₂, R₃ and R₄ are selected from the group consisting ofhydrogen, C₁-C_(100,000)-alkyl, C₂-C_(100,000)-alkenyl andC₆-C_(100,000)-aryl, where the alkyl, alkenyl and aryl are optionallysubstituted with halogen or benzyl ether, and alkylaryl, ester, ketone,alcohol, acid, aldehyde, amide and tosyl containing from 1 to 20 carbonatom, and benzyl ether, alkyl substituted silyl ether where the ethergroup is C₁-C₆ alkylene and alkyl substitution consists of one to threeC₁-C₆ alkyl(s) substituted on silyl, and any other functionality thatthe catalyst referred to below is tolerant of, and where R₂ and R₄ canjoin to form a ring, and X is selected from the group consisting of O, Sand NR₅ where R₅ is selected from the group consisting of hydrogen,C₁-C_(100,000)-alkyl, C₂-C-_(100,000)-alkenyl and C₆-C_(100,000)-arylwhere the alkyl alkenyl and aryl are optionally substituted with halogenor benzyl ether, and alkylaryl, ester, ketone, alcohol, acid, aldehyde,amide and tosyl containing from 1 to 20 carbon atoms, and benzyl ether,alkyl substituted silyl ether where the ether group is C₁-C₆-alkyleneand where the alkyl substitution consists of one to three C₁-C₆ alkyl(s)substituted on silyl, and any other functionality that the catalystreferred to below is tolerant of and does not cause rearrangement, andwhere n is 0 or 1, and Y is C═O or CH₂, said process comprising the stepof reacting compound (I) with carbon monoxide in the presence of acatalytically effective amount of catalyst having the general formula[Lewis acid]^(z+){[QM(CO)_(x)]^(w−)}_(y) where Q is any ligand and neednot be present, M is a transition metal selected from the groupconsisting of Groups 4, 5, 6, 7, 8, 9 and 10 of the periodic table ofelements, z is the valence of the Lewis acid and ranges from 1 to 6, wis the charge of the metal carbonyl and ranges from 1 to 4 and y is anumber such that w times y equals z, and x is a number such as toprovide a stable anionic metal carbonyl for {[QM(CO)_(x)]^(w−)}_(y), toform a product having the structural formula:

where R₁, R₂, R₃ and R₄ and X correspond to R₁, R₂, R₃, R₄ and X in (I)including R₂ and R₄ forming a ring if that is the case for (I); and inthe case where n for (I) is 0, n for (II) is 0 or 1, and in the casewhere n for (I) is 1, n for (II) is 1; said catalyst excluding catalystformed from the combination of a cobalt source and a hydroxy substitutedpyridine.
 2. The process of claim 1 where n for (I) is 0 so that thestructural formula for (I) becomes:

and the product has the structural formula:

n is 1 and Y is C═O.
 3. The process of claim 2 where the catalyst is[(salph)Al(THF)₂][Co(CO)₄] where THF is tetrahydrofuran and which hasthe structural formula:

where So is tetrahydrofuran and ^(t)Bu is t-butyl.
 4. The process ofclaim 3 wherein the reaction is carried out at a carbon monoxidepressure ranging from 100 to 10,000 psi and a temperature ranging from0° to 120° C. in the presence of catalyst in a mole ratio of compound(III) to catalyst (cobalt basis) ranging from 1:1 to 10,000:1.
 5. Theprocess of claim 4 where X for (III) is O.
 6. The process of claim 4where the compound (III) is propylene oxide.
 7. The process of claim 4where the compound (III) is (R)-propylene oxide and the product is(R)-β-butyrolactone.
 8. The process of claim 7 where the reaction iscarried out at a pressure ranging from 850 to 900 psi and a temperatureranging from 0 to 120° C., over a time period ranging from 0.75 to 1.5hours.
 9. The process of claim 4 where the compound (III) is 1-buteneoxide.
 10. The process of claim 4 where the compound (m) isepichlorohydrin.
 11. The process of claim 4 where the compound (m) isisobutylene oxide.
 12. The process of claim 4 where the compound (III)is 2,3-epoxybutane.
 13. The process of claim 4 where X is NR₅.
 14. Theprocess of claim 13 where the compound (III) is 1-benzyl-2-methylaziridine.
 15. The process of claim 13 where the compound (III) is1-tosyl-2-methylaziridine.
 16. The process of claim 13 where thecompound (III) iscis-1-benzyl-2-(tert-butyldimethylsiloxymethyl)-3-methyl aziridine. 17.The process of claim 2 where the catalyst is

where ^(t)Bu is t-butyl and So is tetrahydrofuran.
 18. The process ofclaim 17 where the reaction is carried out at a carbon monoxide pressureranging from 100 to 10,000 psi and a temperature ranging from 0° C. to120° C. in the presence of catalyst in a mole ratio of compound (III) tocatalyst (cobalt basis ranging from 1:1 to 10,000:1.
 19. The process ofclaim 18 where X for (III) is O.
 20. The process of claim 19 where thecompound (III) is benzyl glycidyl ether.
 21. The process of claim 2where the catalyst is

where So is tetrahydrofuran and Ph is phenyl.
 22. The process of claim21 where the reaction is carried out at a carbon monoxide pressureranging from 100 to 10,000 psi and a temperature ranging from 0° C. to120° C. in the presence of catalyst in a mole ratio of compound (III) tocatalyst (cobalt basis) ranging from 1:1 to 10,000:1.
 23. The process ofclaim 22 where X for (III) is O.
 24. The process of claim 23 where thecompound (III) is 1-butene oxide.
 25. The process of claim 23 where thecompound (III) is 1-heptene oxide.
 26. The process of claim 23 where thecompound (III) is cyclooctene oxide.
 27. The process of claim 2 wherethe catalyst has the structure

where M is a metal such that (VI) is stable.
 28. The process of claim 27where the catalyst has the structure (VI) where M is titanium with avalence of three.
 29. The process of claim 28 where the reaction iscarried out at a carbon monoxide pressure ranging from 100 to 10,000 psiand a temperature ranging from 0° C. to 120° C. in the presence of acatalyst in a mole ratio of compound (III) to catalyst (cobalt basis)ranging from 1:1 to 10,000:1.
 30. The process of claim 29 where X forthe compound (III) is O.
 31. The process of claim 30 where the compound(III) is propylene oxide.
 32. The process of claim 31 where the compound(III) is R-propylene oxide.
 33. The process of claim 30 where thecompound (III) is 1,2-epoxybutane.
 34. The process of claim 30 where thecompound (III) is 1,2-epoxy-5-hexene.
 35. The process of claim 30 wherethe compound (III) is epichlorohydrin.
 36. The process of claim 30 wherethe compound (III) is isobutylene oxide.
 37. The process of claim 30where the compound (III) is cis-2,3-epoxybutane.
 38. The process ofclaim 30 where the compound (III) is trans-2,3-epoxybutane.
 39. Theprocess of claim 29 where X for the compound (III) is NR₅.
 40. Theprocess of claim 39 where the compound (III) is 1-benzyl-2-methylaziridine.
 41. Tie process of claim 39 where the compound (III) is7-benzyl-7-azabicyclo[4.1.0]heptane.
 42. The process of claim 39 wherethe compound (III) is 1-tosyl-2-methylaziridine.
 43. The process ofclaim 39 where the compound (III) iscis-1-benzyl-2-(tert-butylmethylsilyloxymethyl)-3-methylaziridine. 44.The process of claim 1 where n for (I) is 1 and Y is C═O or CH₂.
 45. Theprocess of claim 44 where the catalyst has the structure

where THF is tetrahydrofuran and ^(t)Bu is t-butyl and M is Al.
 46. Theprocess of claim 45 where the reaction is carried out at a carbonmonoxide pressure ranging from 100 to 10,000 psi and a temperatureranging from 0° C. to 120° C. in the presence of a catalyst in a moleratio of compound (I) to catalyst (cobalt basis) ranging from 1:1 to10,000:1.
 47. The process of claim 46 where the compound (I) is oxetane.48. The process of claim 46 where Y is C═O and R₁ and R₃ for thecompound (I) are both H.
 49. The process of claim 48 where R₄ for thecompound (I) is H.
 50. The process of claim 49 where R₂ for the compound(I) is Me.
 51. The process of claim 44 where the catalyst has thestructure

where M is titanium with a valence of three.
 52. The process of claim 51where the reaction is carried out at a carbon monoxide pressure rangingfrom 100 to 10,000 psi and a temperature ranging from 0° C. to 120° C.in the presence of a catalyst in a mole ratio of compound (I) tocatalyst (cobalt basis) ranging from 1:1 to 10,000:1.
 53. The process ofclaim 52 where Y is C═O.
 54. The process of claim 53 where R₁, R₃ and R₄for the compound (I) are H.
 55. The process of claim 54 where R₂ for thecompound (I) is Me.
 56. The process of claim 54 where R₂ for thecompound (I) is Et.
 57. The process of claim 54 where R₂ for thecompound (I) is CCl₃.
 58. The process of claim 52 where R₁, R₂ and R₄for the compound (I) are H.
 59. The process of claim 58 where R₃ for thecompound (I) is Me.
 60. The process of claim 58 where R₃ for thecompound (I) is Ph.
 61. The process of claim 44 where the catalyst hasthe structure

where M is samarium with a valence of three.
 62. The process of claim 6where the reaction is carried out at a carbon monoxide pressure rangingfrom 100 to 10,000 psi and a temperature ranging from 0° C. to 120° C.in the presence of a catalyst in a mole ratio of compound (I) tocatalyst (cobalt basis) ranging from 1:1 to 10,000:1.
 63. The process ofclaim 62 where Y is C═CO and R₁, R₃ and R₄ for the compound (I) are Hand R₂ for the compound (I) is Me.
 64. The process of claim 1 where inthe [Lewis acid]^(z+) portion of the catalyst a neutral two electrondonor is present and fills the coordination valence of the cationicLewis acid.
 65. The process of claim 64 where the [Lewis acid]^(z+)portion of the catalyst contains an aluminum or chromium center.
 66. Theprocess claim 65 where the neutral two electron donor istetrahydrofuran.
 67. The process of claim 1 where the catalyst has thestructure

where M is a metal such that (VI) is stable.
 68. The process of claim 67where the reaction is carried out at a carbon monoxide pressure rangingfrom 100 to 10,000 psi and a temperature ranging from 0° C. to 120° C.in the presence of a catalyst in a mole ratio of compound (I) tocatalyst (cobalt basis) ranging from 1:1 to 10,000:1.
 69. A process forthe carbonylation of a compound having the formula

where Ph is phenyl, said process comprising the step of reactingcompound (XI) with carbon monoxide in the presence of a catalyticallyeffective amount of catalyst having the general formula [Lewisacid]^(z+){[QM(CO)_(x)]^(w−)}_(y) where Q is any ligand and need not bepresent, M is a transition metal selected from the group consisting ofGroups 4, 5, 6, 7, 8, 9 and 10 of the periodic table of elements, z isthe valence of the Lewis acid and ranges from 1 to 6, w is the charge ofthe metal carbonyl and ranges from 1 to 4 and y is a number such that wtimes y equals z, and x is a number such as to provide a stable anionicmetal carbonyl for {[QM(CO)_(x)]^(w−)}_(y), to form a product whichcomprises a mixture of


70. A compound having the structural formula:

where ^(t)Bu is t-butyl and So is a neutral two electron donor.
 71. Thecompound of claim 70 where the neutral two electron donor istetrahydrofuran.
 72. A compound having the structural formula:

where the ^(t)Bu is t-butyl and So is a neutral two electron donor. 73.The compound of claim 72 where the neutral two electron donor istetrahydrofuran.
 74. A compound having the structural formula:

where ^(t)Bu is t-butyl and So is a neutral two electron donor.
 75. Thecompound of claim 74 where the neutral two electron donor istetrahydrofuran.
 76. A compound having the structure:

where THF is tetrahydrofuran and ^(t)Bu is t-butyl.
 77. The compound ofclaim 76 where M is Al.
 78. The compound of claim 76 where M is Cr. 79.A compound having the structure:

where ^(t)Bu is t-butyl and So is a neutral two electron donor.
 80. Thecompound of claim 79 where the neutral two electron donor istetrahydrofuran.
 81. A compound having the structure:

where Ph is phenol and So is a neutral two electron donor.
 82. Thecompound of claim 81 where the neutral two electron donor istetrahyrofuran.
 83. 9-Oxa-bicyclo[6.2.0]decan-10-one. 84.13-Oxa-bicyclo[10.2.0]tetradecan-14-one.
 85. The process of claim 1where the [Lewis acid]^(z+) portion of the catalyst does not contain aneutral two electron donor.